Electrochemical and physical properties of LiNixCo1−2xMnxO2 (0.1 ≤ x ≤ 0.33) electrode materials prepared by self-combustion were investigated. Pure LiNixCo1−2xMnxO2 (x = 0.1, 0.2, 0.33) materials with single phase and R-3 m layered structure were obtained as confirmed by X-ray diffraction. Energy Dispersive Spectroscopy, Scanning Electron Microscopy are commonly used to determine the chemical composition and the distribution of particle size of the three samples. The electrochemical performances of the samples were measured at different current rates in the 3-4.5 V potential range. The studied materials exhibit good discharge capacity. The magnetic susceptibility measurements and conventional electronic paramagnetic resonance spectroscopy (EPR, 9.23 GHz) are coupled to probe the valence state of the transition metal ions and to understand their distributions via their magnetic interactions. X-band EPR spectroscopy has been used to study the local environment in the layered LiNixCo1−2xMnxO2. It has been demonstrated that both Ni2+ and Mn4+ ions are paramagnetic while Co3+ exhibits a diamagnetic low-spin configuration in the starting material.